Coordination polymers and hybrid networks of different dimensionalities formed by metal sulfites

In our effort to explore the use of the sulfite ion to design hybrid and open-framework materials, we have been able to prepare, under hydrothermal conditions, zero-dimensional [Zn(C12H8N2)(SO3)]center dot 2H(2)O, I (a = 7.5737(5) angstrom, b = 10.3969(6) angstrom, c = 10.3986(6) angstrom, alpha = 64.172(1)degrees, beta = 69.395(1)degrees, gamma = 79.333(1)degrees, Z = 2, and space group P (1) over bar), one-dimensional [Zn-2(C12H8N2)(SO3)(2)(H2O)], II (a = 8.0247(3) angstrom, b = 9.4962(3) angstrom, c = 10.2740(2) A, alpha = 81.070(1)degrees, beta = 80.438(1)degrees, gamma = 75.66(5)degrees, Z = 2, and space group P (1) over bar), two-dimensional [Zn-2(C10H8N2)(SO3)(2)]center dot H2O, III (a = 16.6062(1) angstrom, b = 4.7935(1) angstrom, c = 19.2721(5) angstrom, beta = 100.674(2)degrees, Z = 4, and space group C2/c), and three-dimensional [Zn-4(C6H12N2)(SO3)(4)(H2O)(4)], IV (a = 11.0793(3) angstrom, c = 8.8246(3) angstrom, Z = 2, and space group P42nm), of which the last three are coordination polymers. A hybrid open-framework sulfite-sulfate of the composition [C2H10N2][Nd(SO3)(SO4)(H2O)](2), V (a = 9.0880(3) angstrom, b = 6.9429(2) angstrom, c = 13.0805(5) A, beta = 91.551(2)degrees, Z = 2, and space group P2(1)/c), with a layered structure containing metal-oxygen-metal bonds has also been described.

Hybrid peptide design. Hydrogen bonded conformations in peptides containing the stereochemically constrained gamma-amino acid residue, gabapentin

he crystal structure of 12 peptides containing the conformationally constrained 1-(aminomethyl)cyclohexaneacetic acid, gabapentin (Gpn), are reported. In all the 39 Gpn residues conformationally characterized so far, the torsion angles about the C-alpha-C-beta and C-beta-C-gamma bonds are restricted to the gauche conformation (+/- 60 degrees). The Gpn residue is constrained to adopt folded conformations resulting in the formation of intramolecularly hydrogen-bonded structures even in short peptides. The peptides Boc-Ac(6)c-Gpn-OMe 1 and Boc-Gpn-Aib-Gpn-Aib-OMe 2 provide examples of C-7 conformation; peptides Boc-Gpn-Aib-OH 3, Boc-Ac(6)c-Gpn-OH 4, Boc-Val-Pro-Gpn-OH 5, Piv-Pro-Gpn-Val-OMe 6, and Boc-Gpn-Gpn-Leu-OMe 7 provide examples of C-9 conformation; peptide Boc-Ala-Aib-Gpn-Aib-Ala-OMe 8 provides an example of C-12 conformation and peptides Boc-beta Leu-Gpn-Val-OMe 9 and Boc-beta Phe-Gpn-Phe-OMe 10 provide examples of C-13 conformation. Gpn peptides provide examples of backbone expanded mimetics for canonical alpha-peptide turns like the gamma (C-7) and the beta (C-10) turns. The hybrid beta gamma sequences provide an example of a mimetic of the C-13 alpha-turn formed by three contiguous alpha-amino acid residues. Two examples of folded tripeptide structures, Boc-Gpn-beta Phe-Leu-OMe 11 and Boc-Aib-Gpn-beta Phg-NHMe 12, lacking internal hydrogen bonds are also presented. An analysis of available Gpn residue conformations provides the basis for future design of folded hybrid peptides.

Melting of an Anchored Bilayer: Molecular Dynamics Simulations of the Structural Transition in (CnH2n+1NH3)(2)PbI4 (n=12, 14, 16, 18)

The thermally driven Structural phase transition in the organic-inorganic hybrid perovskite (CnH2n+1NH3)(2)PbI4 has been investigated using molecular dynamics (MD) simulations. This system consists of positively charged alkyl-amine chains anchored to a rigid negatively charged PbI4 sheet with the chains organized as bilayers with a herringbone arrangement. Atomistic simulations were performed using ail isothermal-isobaric ensemble over a wide temperature range from 65 to 665 K for different alkyl chain lengths, n = 12, 14, 16, and 18. The simulations are able to reproduce the essential Features of the experimental observations of this system, including the existence of a transition, the linear variation of the transition temperature with alkyl chain length, and the expansion of the bilayer thickness at the transition. By use of the distance fluctuation Criteria, it is Shown that the transition is associated With a Melting of the alkyl chains of the anchored bilayer. Ail analysis of the conformation of the alkyl chains shows increased disorder in the form of gauche defects above due melting transition. Simulations also show that the melting transition is characterized by the complete disappearance of all-trans alkyl chains in the anchored bilayer, in agreement with experimental observations. A conformationally disordered chain has a larger effective cross-sectional area, and above due transition a uniformly tilted arrangement of the anchored chains call no longer be Sustained. At the melt the angular distribution of the orientation of the chains are 110 longer uniform; the chains are splayed allowing for increased space for individual chains of the anchored bilayer. This is reflected in a sharp rise in the ratio of the mean head-to-head to tail-to-tail distance of the chains of the bilayer at the transition resulting in in expansion of the bilayer thickness. The present MD simulations provide a simple explanation as to how changes in conformation of individual alkyl-chains gives rise to the observed increase in the interlayer lattice spacing of (CnH2n+1NH3)(2)PbI4 at the melting transition.

Process variability-aware statistical hybrid modeling of dynamic power dissipation in 65 nm CMOS designs

A generalized technique is proposed for modeling the effects of process variations on dynamic power by directly relating the variations in process parameters to variations in dynamic power of a digital circuit. The dynamic power of a 2-input NAND gate is characterized by mixed-mode simulations, to be used as a library element for 65mn gate length technology. The proposed methodology is demonstrated with a multiplier circuit built using the NAND gate library, by characterizing its dynamic power through Monte Carlo analysis. The statistical technique of Response. Surface Methodology (RSM) using Design of Experiments (DOE) and Least Squares Method (LSM), are employed to generate a "hybrid model" for gate power to account for simultaneous variations in multiple process parameters. We demonstrate that our hybrid model based statistical design approach results in considerable savings in the power budget of low power CMOS designs with an error of less than 1%, with significant reductions in uncertainty by atleast 6X on a normalized basis, against worst case design.

Three-dimensional hybrid networks based on aspartic acid

Three-dimensional achiral coordination polymers of the general formula M2(D, l-NHCH (COO)CH2COO)2·C4H4N2 where M = Ni and Co and pyrazine acts as the linker molecule have been prepared under hydrothermal conditions starting with [M(L-NHCH(COO)CH2COO)·3H2O] possessing a helical chain structure. A three-dimensional hybrid compound of the formula Pb2.5[N{CH(COO) CH2COO}22H2O] has also been prepared hydrothermally starting with aspartic acid and Pb(NO3)2. In this lead compound, where a secondary amine formed by the dimerisation of aspartic acid acts as the ligand, there is two-dimensional inorganic connectivity and one-dimensional organic connectivity.

Hybrid peptide hairpins containing alpha- and omega-amino acids: Conformational analysis of decapeptides with unsubstituted beta-, gamma-, and delta-residues at positions 3 and 8

The effects of inserting unsubstituted omega-amino acids into the strand segments of model beta-hairpin peptides was investigated by using four synthetic decapeptides, Boc-Lcu-Val-Xxx-Val-D-Pro-Gly-Leu-Xxx-Val-Val- OMe: pepticle 1 (Xxx=Gly), pepticle 2 (Xxx=beta Gly=beta hGly=homoglycine, beta-glycine), pepticle 3 (Xxx=gamma Abu=gamma-aminobutyric acid), pepticle 4 (Xxx= delta Ava=delta-aminovaleric acid). H-1 NMR studies (500 MHz, methanol) reveal several critical cross-strand NOEs, providing evidence for P-hairpin conformations in peptides 2-4. In peptide 3, the NMR results support the formation of the nucleating turn, however, evidence for cross-strand registry is not detected. Single-crystal X-ray diffraction studies of peptide 3 reveal a beta-hairpin conformation for both molecules in the crystallographic asymmetric unit, stabilized by four cross-strand hydrogen bonds, with the gamma Abu residues accommodated within the strands. The D-Pro-Gly segment in both molecules (A,B) adopts a type II' beta-turn conformation. The circular dichroism spectrum for peptide 3 is characterized by a negative CD band at 229 rim, whereas for peptides 2 and 4, the negative band is centered at 225 nm, suggesting a correlation between the orientation of the amide units in the strand segments and the observed CD pattern.

Polypeptide Helices in Hybrid Peptide Sequences

A new class of polypeptide helices in hybrid sequences containing alpha-, beta-, and gamma-residues is described. The molecular conformations in crystals determined for the synthetic peptides Boc-Leu-Phe-Val-Aib-beta Phe-Leu-Phe-Val-OMe 1 (beta Phe: (S)-beta(3)-homophenylalanine) and Boc-Aib-Gpn-AibGpn-OM2(Gpn:1-(aminomethyl)cycl hexaneacetic acid) reveal expanded helical turns in the hybrid sequences (alpha alpha beta)(n) and (ay), In 1, a repetitive helical structure composed Of C-14 hydrogen-bonded units is observed, whereas 2 provides an example of a repetitive C-12 hydrogen-bonded structure. Using experimentally determined backbone torsion angles for the hydrogen-bonded units formed by hybrid sequences, we have generated energetically favorable hybrid helices. Conformational parameters are provided for C-11, C-12, C-13, C-14, and C-15 helices in hybrid sequences.

Multiple conformational states in crystals and in solution in alpha gamma hybrid peptides. Fragility of the C-12 helix in short sequences

The conformational properties of foldamers generated from alpha gamma hybrid peptide sequences have been probed in the model sequence Boc-Aib-Gpn-Aib-Gpn-NHMe. The choice of alpha-aminoisobutyryl (Aib) and gabapentin (Gpn) residues greatly restricts sterically accessible coil formational space. This model sequence was anticipated to be a short segment of the alpha gamma C-12 helix, stabilized by three successive 4 -> 1 hydrogen bonds, corresponding to a backbone-expanded analogue of the alpha polypeptide 3(10)-helix. Unexpectedly, three distinct crystalline polymorphs were characterized in the solid state by X-ray diffraction. In one form, two successive C-12 hydrogen bonds were obtained at the N-terminus, while a novel C-17 hydrogen-bonded gamma alpha gamma turn was observed at the C-terminus. In the other two polymorphs, isolated C-9 and C-7 hydrogen-bonded turns were observed at Gpn (2) and Gpn (4). Isolated C-12 and C-9 turns were also crystallographically established in the peptides Boc-Aib-Gpn-Aib-OMe and Boc-Gpn-Aib-NHMe, respectively. Selective line broadening of NH resonances and the observation of medium range NH(i)<-> NH(i+2) NOEs established the presence of conformational heterogeneity for the tetrapeptide in CDCl3 solution. The NMR results are consistent with the limited population of the continuous C-12 helix conformation. Lengthening of the (alpha gamma)(n) sequences in the nonapeptides Boc-Aib-Gpn-Aib-Gpn-Aib-Gpn-Aib-Gpn-Xxx (Xxx = Aib, Leu) resulted in the observation of all of the sequential NOEs characteristic of an alpha gamma C-12 helix. These results establish that conformational fragility is manifested in short hybrid alpha gamma sequences despite the choice of conformationally constrained residues, while stable helices are formed on chain extension.

A hybrid computer for X-ray crystallography

A hybrid computer for structure factor calculations in X-ray crystallography is described. The computer can calculate three-dimensional structure factors of up to 24 atoms in a single run and can generate the scatter functions of well over 100 atoms using Vand et al., or Forsyth and Wells approximations. The computer is essentially a digital computer with analog function generators, thus combining to advantage the economic data storage of digital systems and simple computing circuitry of analog systems. The digital part serially selects the data, computes and feeds the arguments into specially developed high precision digital-analog function generators, the outputs of which being d.c. voltages, are further processed by analog circuits and finally the sequential adder, which employs a novel digital voltmeter circuit, converts them back into digital form and accumulates them in a dekatron counter which displays the final result. The computer is also capable of carrying out 1-, 2-, or 3-dimensional Fourier summation, although in this case, the lack of sufficient storage space for the large number of coefficients involved, is a serious limitation at present.

Chemical Aspects of the Synergistic Hypergolic Ignition in Hybrid Systems with N2O4 as Oxidizer

Synergistic hypergolic ignition with nitrogen tetroxide ( N2O4) as oxidizer has been observed in hybrid systems comprising of a mixture of magnesium and Schiff bases as fuels. The ignition delays (IDs) measured using a modified device, have been compared with those of magnesium-Schiff base-WFNA systems under identical conditions. The ID has been found to vary with the nature of the substitution in both the benzene rings. A linear relationship emerges when the ignition delays are plotted against the Hammett substitution constants (σ). The preignition products of the reaction of N2O4 with magnesium and benzylidineaniline have been analysed to be Mg(NO3)2, benzenediazonium salt and benzaldehyde. Based on the preignition products isolated, a probable reaction mechanism has been proposed. The previously proposed preignition mechanism for the Schiff base-magnesium-WFNA system has been further supported from the present ignition delay data.

A hybrid electrochemical-thermal method for the preparation of large ZnO nanoparticles

A simple and efficient two-step hybrid electrochemical-thermal route was developed for the synthesis of large quantity of ZnO nanoparticles using aqueous sodium bicarbonate electrolyte and sacrificial Zn anode and cathode in an undivided cell under galvanostatic mode at room temperature. The bath concentration and current density were varied from 30 to 120 mmol and 0.05 to 1.5 A/dm(2). The electrochemically generated precursor was calcined for an hour at different range of temperature from 140 to 600 A degrees C. The calcined samples were characterized by XRD, SEM/EDX, TEM, TG-DTA, FT-IR, and UV-Vis spectral methods. Rietveld refinement of X-ray data indicates that the calcined compound exhibits hexagonal (Wurtzite) structure with space group of P63mc (No. 186). The crystallite sizes were in the range of 22-75 nm based on Debye-Scherrer equation. The TEM results reveal that the particle sizes were in the order of 30-40 nm. The blue shift was noticed in UV-Vis absorption spectra, the band gaps were found to be 5.40-5.11 eV. Scanning electron micrographs suggest that all the samples were randomly oriented granular morphology.

Synthesis, Structure, and Solid-State Transformation Studies of Phosphonoacetate Based Hybrid Compounds of Uranium and Thorium

Three new phosphonoacetate hybrid frameworks based on the actinide elements uranium and thorium have been synthesized. The compounds [C4N2H14][(UO2)(2)(O3PCH2COO)(2)]center dot H2O, I,[C4N2H14][(UO2)(2)(C2O4)(O3PCH2COOH)(2)], II, and Th(H2O)(2)(O3PCH2COO)(C2O4)(0.5). H2O, III, are built up from the connectivity between the metal polyhedra and the phosphonoacetate/oxalate units. Compound II has been prepared using a solvent-free approach, by a solid state reaction at 150 degrees C. It has been shown that II can also be prepared through a room temperature mechanochemical (grinding) route. The layer arrangement in III closely resembles to that observed in I. The compounds have been characterized by powder X-ray diffraction, IR spectroscopy, thermogravimetric analysis, and fluorescence studies.

Conformational properties of hybrid peptides containing alpha and omega-amino acids

This review briefly surveys the conformational properties of guest omega-amino acid residues when incorporated into host alpha-peptide sequences. The results presented focus primarily on the use of beta- and gamma-residues in alphaomega sequences. The insertion of additional methylene groups into peptide backbones enhances the range of accessible conformations, introducing additional torsional variables. A nomenclature system, which permits ready comparisons between alpha-peptides and hybrid sequences, is defined. Crystal structure determination of hybrid peptides, which adopt helical and beta-hairpin conformations permits the characterization of backbone conformational parameters for beta- and gamma-residues inserted into regular alpha-polypeptide structures. Substituted beta- and gamma-residues are more limited in the range of accessible conformation than their unsubstituted counterparts. The achiral beta,beta-disubstituted gamma-amino acid, gabapentin, is an example of a stereochemically constrained residue in which the torsion angles about the C-beta-C-gamma (theta(1)) and C-alpha-C-beta (theta(2)) bonds are restricted to the gauche conformation. Hybrid sequences permit the design of novel hydrogen bonded rings in peptide structures.

A review of hybrid rockets: present status and future potential

This paper discusses the potential of the hybrid rocket engine as a viable and attractive mode of propulsion for both space vehicles and missiles. Research and development work on this engine in other countries is presented and evaluated. The various advantages of a hybrid engine over solid and liquid engines and its problems are highlighted. It has been argued that because of the low technology needed in the development of the hybrid system, it constitutes a cost-and-time-effective propulsion system for several applications in space programmes as well as weapon systems. In support of this conclusion, experience on the developmental studies of a variable thrust 100 kg engine is presented. Some future possibilities for hybrid propulsion systems are cited.

Nonlinear Transport in Hybrid Polypyrrole-Gold Nanostructures

We have studied charge transport in nanometer scale films of polypyrrole (PPy) that were grown electrochemically onto discontinuous ultrathin films of gold. The gold films consisted of 100 nm size islands, separated from each other by nanometer-size gaps. The thickness of PPy can be varied from 30 to 200 nm. The I-V characteristics of these hybrid PPy-Au nanostructures show strong non-linearity at low temperatures, and in particular for the more insulating samples. The hopping transport is further verified from the log / versus V-1/4 plots. Furthermore, the I-V data follow an empirical relation dlog//dV(1/4) similar to T-1/2.